CN115703858B - Propylene copolymer, and preparation method and application thereof - Google Patents
Propylene copolymer, and preparation method and application thereof Download PDFInfo
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- CN115703858B CN115703858B CN202110945730.9A CN202110945730A CN115703858B CN 115703858 B CN115703858 B CN 115703858B CN 202110945730 A CN202110945730 A CN 202110945730A CN 115703858 B CN115703858 B CN 115703858B
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 229920001577 copolymer Polymers 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 364
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 82
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 69
- -1 polypropylene Polymers 0.000 claims abstract description 45
- 229920001155 polypropylene Polymers 0.000 claims abstract description 42
- 239000004743 Polypropylene Substances 0.000 claims abstract description 37
- 206010051246 Photodermatosis Diseases 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 110
- 239000000178 monomer Substances 0.000 claims description 100
- 150000001336 alkenes Chemical class 0.000 claims description 86
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 84
- 238000006243 chemical reaction Methods 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 76
- 230000008569 process Effects 0.000 claims description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 38
- 239000002685 polymerization catalyst Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000005977 Ethylene Substances 0.000 claims description 16
- 239000011541 reaction mixture Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 230000003139 buffering effect Effects 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 8
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 230000008845 photoaging Effects 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Chemical group 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical group [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Chemical group 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052727 yttrium Chemical group 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229920006112 polar polymer Polymers 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 229920000642 polymer Polymers 0.000 description 42
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 238000007334 copolymerization reaction Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 16
- 230000032683 aging Effects 0.000 description 14
- 239000012752 auxiliary agent Substances 0.000 description 14
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 12
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 238000013461 design Methods 0.000 description 11
- 238000012662 bulk polymerization Methods 0.000 description 10
- 229920000098 polyolefin Polymers 0.000 description 10
- 238000011056 performance test Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
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- 150000001875 compounds Chemical class 0.000 description 4
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- 239000012968 metallocene catalyst Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229920005606 polypropylene copolymer Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 238000010557 suspension polymerization reaction Methods 0.000 description 2
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
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- 229920001400 block copolymer Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000010924 continuous production Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a propylene copolymer, which comprises a polymerization sequence of propylene units and a polymerization sequence of acrylonitrile units on a molecular main chain, wherein the polymerization sequence of the propylene units and the polymerization sequence of the acrylonitrile units are alternately arranged, and the structural formula is as follows:wherein, m ', n and n' are positive integers, m: n is 20-100:1, m': n' is 20-100:1. The invention also relates to a preparation method of the propylene copolymer, and a compatilizer, a binder, an anti-photoaging polypropylene resin and an anti-static polypropylene resin containing the propylene copolymer for outdoor products. The propylene copolymer provided by the invention has good compatibility and cohesiveness when being blended with other polar polymers, meanwhile, the antistatic property of polypropylene is improved, and the copolymer can keep the excellent property for a long time.
Description
Technical Field
The invention belongs to the technical field of polymer preparation, and particularly relates to a propylene copolymer, and a preparation method and application thereof.
Background
Polypropylene is one of the most widely used polymers at present, has excellent mechanical properties and processability, is also a recognized environment-friendly material, and can be completely degraded in natural environment under certain conditions. However, polypropylene has the biggest disadvantage that it is susceptible to photo-aging such that both the lifetime and the range of applications of the material are greatly limited.
For many years, many researchers have desired to solve the technical problem of photo-aging polypropylene. Some researchers have desired to introduce some polar groups into polypropylene molecules by chemical modification to improve its photoaging properties. However, since the polypropylene molecule is a nonpolar molecule, it is not easy to graft a large amount of polar group-containing monomers into the polypropylene molecule by chemical modification means such as grafting.
Some researchers have also desired to blend it with polymers or adjuvants with good photo-aging properties by physical modification to improve their properties. The blending method in the prior art is to blend two or more copolymers with different properties after respectively polymerizing the polymers to obtain the copolymers with different properties, so as to obtain the olefin copolymer composition; the olefin polymers of this method modify the properties of the polymers by blending, but on the one hand, it is difficult to compatibilize polymers of different polarities, and since the molecules of the polymers themselves have fluidity, even though the polymers which are temporarily made to be compatible together appear to be able to meet the requirements of the properties, the molecules of the different polymers migrate with each other over time, and in severe cases the molecules constituting the blend may migrate into two phases, severely affecting the properties of the product.
It has also been reported that different polymers can be prepared by reactor blending, i.e., in different reactors, and then flowing together the melts or solutions of the various polymers to blend them, which is more uniform in performance than a typical melt blend; however, such a reactor blend still has difficulty in fundamentally obtaining high value-added olefin polymers excellent in comprehensive properties at the level of molecular structure.
Disclosure of Invention
Based on the above, the main object of the present invention is to provide a propylene copolymer and a preparation method thereof, wherein the propylene copolymer has excellent comprehensive performance, and the preparation method of the propylene copolymer is characterized in that different reaction conditions are suitable for different processes by controlling polymerization reaction, so that the polymerization process is switched under different reaction conditions according to process design, thereby controlling the molecular structure of the polymer to grow according to the designed molecular chain, and obtaining the propylene copolymer with excellent comprehensive performance; meanwhile, the preparation method of the propylene copolymer ensures that the catalyst components introduced into the polymerization reactor are uniform and the temperature and pressure are consistent with those of the polymerization reactor by controlling the feeding method of the catalyst, reduces the influence of the catalyst feeding procedure on the polymerization reaction to the minimum extent, ensures that the process condition of the polymerization reaction is controlled, prepares the high-performance polyolefin with a designable molecular structure, improves the uniformity and the comprehensive performance of the molecular structure of the product, and simultaneously can avoid the blockage of a feeding pipeline and improve the production efficiency, thereby being more suitable for practical use.
To this end, the present invention provides a propylene copolymer comprising a polymerization sequence of propylene units and a polymerization sequence of acrylonitrile units on a molecular main chain, the polymerization sequence of propylene units and the polymerization sequence of acrylonitrile units being alternately arranged, and having the structural formula:
wherein, m ', n and n' are positive integers, m: n is 20-100:1, m': n' is 20-100:1.
Preferably, the aforementioned propylene copolymer, wherein the polymerized sequence of the acrylonitrile unit comprises a polymerized sequence located in the middle of the molecular chain and a polymerized sequence located at the end of the molecular chain; wherein the content of the polymeric sequence positioned in the middle of the molecular chain is larger than that of the polymeric sequence positioned at the end of the molecular chain.
Preferably, the aforementioned propylene copolymer, wherein the percentage of the acrylonitrile unit is 1.0% to 5.0% in terms of molar ratio.
Preferably, the aforementioned propylene copolymer, wherein the propylene copolymer has a weight average molecular weight of 50000 ～ 1000000.
Preferably, the aforementioned propylene copolymers, wherein the melt index is from 10 to 40g/10min, measured according to ASTM D1238.
The invention also provides a preparation method of the propylene copolymer, wherein the molecular main chain of the propylene copolymer comprises a polymerization sequence of propylene units and a polymerization sequence of acrylonitrile units, and the polymerization sequences of the propylene units and the polymerization sequences of the acrylonitrile units are alternately arranged; the preparation method of the propylene copolymer comprises the following steps:
(1) Introducing a first olefin monomer into a polymerization reactor in the presence of a propylene polymerization catalyst to polymerize the first olefin monomer under first polymerization conditions;
(2) Introducing a second olefin monomer into the reaction mixture of step (1) in the presence of a propylene polymerization catalyst, and polymerizing under second polymerization conditions;
(3) Introducing a first olefin monomer into the reaction mixture of step (2) in the presence of a propylene polymerization catalyst, so that the first olefin monomer is polymerized under first polymerization conditions;
(4) Repeating the step (2) and the step (3) for 2-5 times;
(5) Adding a chain terminator to terminate the reaction, filtering and washing to obtain the propylene copolymer.
Preferably, the aforementioned method further comprises the steps of:
(11) Uniformly mixing a propylene polymerization catalyst and a solvent to obtain a catalyst premix;
(12) The catalyst premix is sequentially metered, conveyed and buffered and then is introduced into a polymerization reactor to polymerize a first olefin monomer under the first polymerization condition, and then a second olefin monomer is added to polymerize the second olefin monomer under the second polymerization condition; wherein the metering, the delivering and the buffering of the premix liquid components are controlled to be uniform, and the pressure of the buffer tank is controlled to be the same as the pressure in the polymerization reactor.
Preferably, the aforementioned process, wherein said first polymerization conditions and said second polymerization conditions are alternately carried out in a spatial sequence in the same polymerization reactor; two reaction areas with independently controlled reaction conditions are arranged in the polymerization reactor; each of the reaction zones is provided with a catalyst feed system.
Preferably, the aforementioned process, wherein said first polymerization conditions and said second polymerization conditions are respectively carried out alternately in a spatial sequence in two polymerization reactors connected in series; the polymerization reactors are each provided with a catalyst feed system.
Preferably, the foregoing method, wherein said metering comprises metering the catalyst premix liquid in a metering tank; the metering tank is equipped with a stirring cycle and is precisely metered by means of a diaphragm metering pump.
Preferably, in the foregoing method, the conveying adopts a pipeline provided with a stirrer with a pipeline structure.
Preferably, the method as described above, wherein buffering comprises agitating the catalyst premix in a buffer tank and circulating and adjusting the temperature of the premix, the pressure within the buffer tank.
Preferably, the foregoing process, wherein the propylene polymerization catalyst comprises a main catalyst and a cocatalyst; wherein, the chemical structural formula of the main catalyst is shown as the following formula:
In the above, R 1 And R is 2 Each independently selected from one of C1-C20 alkyl, C3-C20 cycloalkyl and C6-C20 aryl; r is R 3 And R is R 4 The two groups are identical or different and are respectively and independently selected from one of hydrogen atoms, C1-C20 alkyl groups, C3-C20 cycloalkyl groups and C6-C20 aryl groups; x is selected from Cl, br, methyl or ethyl; m is selected from titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium; the cocatalyst comprises an organometallic aluminium compound; further preferably, the cocatalyst is at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum or methylaluminoxane; the ratio of the cocatalyst to the main catalyst is 200-800:1 in terms of mass ratio.
Preferably, the aforementioned method, wherein the solvent is selected from at least one of n-hexane, n-heptane or toluene.
Preferably, the method as described above, wherein the chain terminator is an ethanol solution of hydrochloric acid.
Preferably, the aforementioned process wherein the first olefin monomer is selected from propylene, or a mixture of propylene and ethylene, further preferably, the molar content of propylene in the mixture is greater than or equal to 96%; the second olefinic monomer is selected from acrylonitrile monomers.
Preferably, the aforementioned method, wherein the reaction temperature and reaction pressure of the first polymerization condition and the second polymerization condition are the same or different; the first polymerization conditions are: the reaction temperature is 40-75 ℃, and the reaction pressure is 0.5-3.0 Mpa; the second polymerization conditions are: the reaction temperature is 60-90 ℃, and the reaction pressure is 2.0-4.0 Mpa.
Preferably, the aforementioned method, wherein the first polymerization condition and the second polymerization condition are both reactions under an inert gas atmosphere.
The invention also provides a compatilizer which comprises the propylene copolymer and is applied to the polyacrylonitrile and polypropylene blend to improve the compatibility of the polyacrylonitrile and the polypropylene blend.
The invention also provides an adhesive, which comprises the propylene copolymer and is applied to the adhesion of the polypropylene material and the polar polypropylene material so as to improve the adhesion force of the polypropylene material and the polar polypropylene material.
The invention also provides a photo-aging resistant polypropylene resin for outdoor products, which comprises the propylene copolymer.
The invention also provides antistatic polypropylene resin which comprises the propylene copolymer.
By means of the technical scheme, the propylene copolymer provided by the invention and the preparation method and application thereof have at least the following advantages:
1. According to the preparation method of the propylene copolymer, the polymerization reaction is switched under the first polymerization condition and the second polymerization condition through the process design, and is alternately carried out, so that the molecular chains of the polymer grow into different structures in different polymerization stages, and the propylene copolymer with stable molecular structure and controlled product performance is obtained;
2. according to the propylene copolymer provided by the invention, cyano groups are introduced into a main chain structure of a polypropylene molecule in a certain sequence and in a certain quantity, so that the propylene copolymer shows good compatibility and cohesiveness when being blended with other polar polymers, meanwhile, the antistatic property of polypropylene is improved, and the copolymer can keep the excellent performance for a long time;
3. the preparation method of the propylene copolymer provided by the invention can effectively catalyze the copolymerization of propylene or the mixture of propylene and ethylene and acrylonitrile monomers by reasonably selecting and applying the total heterocyclic non-metallocene compound as the catalyst, has high activity and excellent copolymerization performance, and can be used for structural design of high-added-value products such as the propylene copolymer and the like and polymer manufacturing process to obtain the propylene copolymer with excellent comprehensive performance.
Drawings
FIG. 1 is a schematic process flow diagram of the process for preparing propylene copolymers of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The propylene copolymer provided by the invention comprises a polymerization sequence of propylene units and a polymerization sequence of acrylonitrile units on a molecular main chain; the polymerization sequences of the propylene units are alternately arranged with the polymerization sequences of the acrylonitrile units; the structural formula is as follows:
wherein, m ', n and n' are positive integers, m: n is 20-100:1, m': n' is 20-100:1.
From the structural view, cyano (CN) in the acrylonitrile is taken as a strong electron withdrawing group, has carbon-nitrogen triple bonds with stronger polarity, and has the volume of only 1/8 of that of methyl; the carbon and nitrogen atoms are linked by a triple bond (one sigma and two pi) which imparts a relatively high stability to the cyano group, so that it is present as a whole in a typical chemical reaction. In the propylene polymer, the acrylonitrile unit is connected into the molecular chain main chain of the polymer in a form of opening double bonds. In the propylene polymer, the acrylonitrile units can be positioned at the end of the molecular chain, but in general, the number of the acrylonitrile units connected to the main chain of the molecular chain is larger than that of the acrylonitrile units connected to the end of the molecular chain, and the connection length and the connection position can be designed and controlled through technological parameters.
Preferably, the polymerization sequence of the acrylonitrile unit comprises a polymerization sequence positioned in the middle of a molecular chain and a polymerization sequence positioned at the end of the molecular chain; wherein the content of the polymerization sequence positioned in the middle of the molecular chain is larger than that of the polymerization sequence positioned at the end part of the molecular chain; or the polymerized sequence of the acrylonitrile unit is positioned in the middle of the molecular chain; the polymerization sequence in the middle of the molecular chain is that different polymerization sequences are connected to two sides of the polymerization sequence; the polymeric sequence at the end of the molecular chain means that a different polymeric sequence is attached to only one side thereof.
The access position and the access quantity of the acrylonitrile units pass 13 The measurement was performed by the method of C nuclear magnetic resonance.
The polymerization sequence of the acrylonitrile unit is in a spiral space three-dimensional conformation and is mainly determined by a lateral group-cyano group (CN) with stronger polarity and larger volume. The carbon and nitrogen atoms in the cyano group are connected by trivalent bonds, and the structure can absorb photons (ultraviolet light) with more energy and can be converted into heat energy, so that the main bonds are protected, and the main bonds are not easy to degrade. Therefore, the polypropylene copolymer modified by cyano group has good stability to sunlight and atmospheric effects. After one year of sunlight and atmosphere, the strength of most fibers can lose 90% -95% of the original strength, and the strength reduction rate of the propylene copolymer is less than or equal to 30%.
Preferably, the percentage content of the acrylonitrile unit is 1.0-5.0% in terms of mole ratio.
The number of the acrylonitrile units in the main chain of the grafting molecule should reach a certain content so as to achieve the effect of modification, but the grafting amount of the number of the acrylonitrile units is not too high, on one hand, from the aspect of cost, and on the other hand, the grafting amount is also used for avoiding influencing the own excellent performance of the polypropylene when the content of the grafting acrylonitrile is large.
Preferably, the propylene copolymer has a weight average molecular weight of 50000 ～ 1000000.
According to the technical scheme, the acrylonitrile unit is connected into the main chain of the molecular chain of the copolymer, so that the molecular structure and the comprehensive performance of the propylene copolymer are in a controlled state, and the molecular structure and the comprehensive performance of the propylene copolymer are basically consistent with the design performance of technicians. If the time and position of acrylonitrile access are not controlled from the preparation process, but only the ends of molecular chains are randomly accessed, in order to ensure that a sufficient number of acrylonitrile units can be contained in the copolymer, the molecular weight of the copolymer is greatly reduced, or the polymerization sequence of acrylonitrile units and the polymerization sequence of propylene units are respectively polymerized into longer molecular chains, which are difficult to form a stable and controlled molecular structure from the microstructure, and have a great influence on the performance of the product.
The molecular weight distribution of the propylene copolymer was evaluated by gel chromatography (GPC).
Preferably, it has a melt index of 10 to 40g/10min as measured according to ASTM D1238.
The invention provides a preparation method of a propylene copolymer, wherein a molecular main chain of the propylene copolymer comprises a polymerization sequence of a propylene unit and a polymerization sequence of an acrylonitrile unit; the polymerization sequences of the propylene units are alternately arranged with the polymerization sequences of the acrylonitrile units; the preparation method of the propylene copolymer comprises the following steps:
1) Introducing a first olefin monomer into a polymerization reactor in the presence of a propylene polymerization catalyst to polymerize the first olefin monomer under first polymerization conditions;
2) Introducing a second olefin monomer into the reaction mixture in the presence of a propylene polymerization catalyst, and polymerizing the second olefin monomer under a second polymerization condition;
3) Introducing a first olefin monomer into the reaction mixture in the presence of a propylene polymerization catalyst to polymerize the first olefin monomer under first polymerization conditions;
4) Executing the step 2) and the step 3) for 2-5 times;
5) Adding a chain terminator to terminate the reaction, filtering and washing to obtain the propylene copolymer.
Preferably, the preparation method further comprises the following steps:
11 Uniformly mixing a propylene polymerization catalyst with a solvent to obtain a catalyst premix; 12 The catalyst premix is sequentially metered, conveyed and buffered and then is introduced into a polymerization reactor to polymerize a first olefin monomer under the first polymerization condition and polymerize a second olefin monomer under the second polymerization condition respectively; wherein the metering, the delivering and the buffering of the premix liquid components are controlled to be uniform, and the buffering pressure is controlled to be the same as the pressure in the polymerization reactor.
For convenience of description, in the polymerization process of the present invention, polymerization performed under the first polymerization condition is defined as a first polymerization; the polymerization carried out under the second polymerization conditions is defined as a second polymerization. The first polymerization and the second polymerization are reacted according to a process design sequence.
The first polymerization comprises polymerizing a catalyst with a first olefin monomer; alternatively, the first polymerization includes polymerizing the catalyst with the first olefin monomer and the reaction mixture. The second polymerization includes polymerizing a catalyst with a second olefin monomer and a reaction mixture. The first aggregation and the second aggregation occur alternately in a time sequence or a spatial sequence. And a certain auxiliary agent can be added into the first polymerization and the second polymerization according to actual needs, so that the reaction conditions in the polymerization process can be controlled or regulated to control the properties of the product. The first auxiliary agent is introduced into a polymerization reactor together with the first olefin monomer in the first polymerization process; and a second auxiliary agent is introduced into the polymerization reactor together with the second olefin monomer in the second polymerization process.
In the prior art, the polymerization modes of the polymer mainly comprise suspension polymerization, emulsion polymerization, bulk polymerization and solution polymerization. At present, the processes of suspension polymerization and emulsion polymerization have been developed quite perfectly, the maximization is realized, the cost is close to the limit, the universality of the method is smaller, the possibility of further development is smaller from the technical point of view, and the method can only be used as the production process of the characteristic polymer in the future; however, bulk polymerization and solution polymerization have technical problems yet to be solved, but these two methods have strong versatility, so with the development of science and technology, the polymer manufacturing process gradually progresses toward bulk polymerization and solution polymerization.
The polymerization process of the present invention may be selected according to the form of the target product, and bulk polymerization or solution polymerization is preferably used.
When the product is required to be in solution form, for example for use as an adhesive, then both the first and second polymerizations are solution polymerizations. In the solution polymerization, the viscosity of the reaction system is reduced due to the use of the solvent, which is very favorable for mixing materials and transferring heat, so that the solution polymerization still has good development prospect from the development point of view because the solution polymerization has strong universality and is easy to realize large-scale and continuous production, although the solvent recovery and treatment procedures are increased and the solvent can pollute the environment and the like due to the use of the solvent. The technical scheme of the invention is that the propylene copolymer is preferably prepared by the full-heterocyclic non-metallocene compound, is suitable for a solution polymerization method, can effectively catalyze propylene to be homopolymerized, propylene to be copolymerized with ethylene to be copolymerized with acrylonitrile monomers, has high catalytic activity and excellent copolymerization performance, and can gradually polymerize by the technical scheme of the invention to obtain polyolefin products with high added values.
When the product is in the form of a polypropylene powder, for example when used as a resin, then both the first and second polymerizations are bulk polymerizations. In the bulk polymerization, the catalyst suspension may be pre-polymerized with the propylene monomer in advance in order to easily control the reaction severity in the bulk polymerization, maintaining the stability of the reaction conditions. The technical scheme of the invention is that the propylene copolymer is preferably prepared by the full-heterocyclic non-metallocene compound, is suitable for a solution polymerization method, can effectively catalyze propylene to be homopolymerized, propylene to be copolymerized with ethylene to be copolymerized with acrylonitrile monomers, has high catalytic activity and excellent copolymerization performance, and can gradually polymerize by the technical scheme of the invention to obtain polyolefin products with high added values.
The first polymerization and the second polymerization may be alternately reacted in time series in the same polymerization reactor; the polymerization reactor is provided with a catalyst feed system. When the first polymerization and the second polymerization occur in the same polymerization reactor, the first polymerization and the second polymerization may be alternately performed in time series, that is, in accordance with "first polymerization-reaction condition switching-second polymerization-reaction condition switching-first polymerization … …"; such a reaction route affects the control of the reaction conditions because of the transition period when the reaction conditions are switched, but has the advantage of simple equipment and small space occupation.
The first polymerization and the second polymerization may alternatively react in a spatial sequence in the same polymerization reactor; two reaction areas with independently controlled reaction conditions are arranged in the polymerization reactor; each of the reaction zones is provided with a catalyst feed system. When at least two reaction areas with independently controlled reaction conditions are arranged in the polymerization reactor, the first polymerization and the second polymerization can be alternately performed in the polymerization reactor according to a space sequence, namely, two areas with independently controlled reaction conditions are arranged in the same reactor, the first polymerization is performed in one area, and the second polymerization is performed in the other area; according to the designed reaction route, the reaction materials alternately undergo a first polymerization reaction and a second polymerization reaction in different areas. In the technical scheme of the invention, the internal detailed structure of the polymerization reactor is not particularly limited, so long as the automatic transfer of the materials between the two reaction areas according to the set process time can be realized.
The first polymerization and the second polymerization may also be reacted in a spatial sequence in two polymerization reactors connected in series, respectively; the polymerization reactors are each provided with a catalyst feed system. When the first polymerization and the second polymerization respectively take place in two polymerization reactors connected to each other in series, the materials between the two polymerization reactors can be transferred to each other, the first polymerization and the second polymerization being alternately performed, that is: first polymerization-mass transfer-second polymerization-mass transfer-first polymerization … …, the reactions are cycled in sequence.
As shown in fig. 1, the technical scheme of the invention adopts the illustrated process flow, catalyst batching is firstly carried out, catalyst is proportioned and manufactured according to a designed formula, and then catalyst is metered and buffered and then introduced into a polymerization reactor, and stirring devices are arranged on the batching, metering, buffering and conveying pipelines among all parts so as to keep the components of the catalyst uniform all the time, prevent the catalyst from influencing the component uniformity due to catalyst sedimentation and avoid production faults such as blockage of conveying pipelines and the like caused by catalyst sedimentation; the catalyst is respectively connected with the polymerization reactor of the first polymerization and the polymerization reactor of the second polymerization, and can provide the catalyst with uniform components and accurate metering for the polymerization reactors so as to accurately control the quantity and the speed of the catalyst addition. The polymerization is divided into a first polymerization and a second polymerization, wherein a first auxiliary agent, a first olefin monomer and a catalyst are introduced into a polymerization reactor according to a designed formula to be polymerized under a first polymerization condition; the first olefin monomer may be dissolved or dispersed in a solvent prior to being fed to the polymerization reactor; when the first olefin monomer is a gaseous monomer, then the first olefin monomer is introduced directly into the polymerization reactor so that it is dissolved in the reaction mixture. Prior to mixing, it is often necessary to purge the solvent and first olefin monomer to remove potential catalyst poisons. The reaction mixture is switched to a second polymerization condition, and a propylene polymerization catalyst, a second olefin monomer and a second auxiliary agent are added for polymerization. The second olefin monomer may be dissolved or dispersed in a solvent prior to being fed to the second polymerization reactor; when the second olefin monomer is a gaseous monomer, then the second olefin monomer is introduced directly into the polymerization reactor so that it is dissolved in the reaction mixture. Prior to mixing, it is often necessary to purge the solvent and the second olefin monomer to remove potential catalyst poisons. And switching the reaction mixture to a first polymerization condition, and adding a propylene polymerization catalyst, a first olefin monomer and a first auxiliary agent for polymerization. The process parameters and the cycle times of polymerization reversal are designed according to the molecular weight and the like of the target polymer.
The polymerization reactor is provided with a control center; the control center can receive process control parameters input by engineering technicians and can also monitor the polymerization reaction process in real time; in the polymerization reaction process, the control center compares the actual situation of the polymerization reaction with the preset cycle times to judge whether the polymerization reaction reaches the set condition, if the polymerization reaction reaches the set condition, the polymerization reaction is ended, and then a chain terminator is added to stop the reaction; if the polymerization reaction has not reached the set condition, the cycle is performed "polymerization under the second polymerization condition-polymerization under the first polymerization condition".
The polymerization conditions may be determined according to the design of the process route, and for example, the conditions for the first polymerization may be set, including at least the kind and amount of the first olefin monomer and the first auxiliary agent, the reaction temperature, the reaction pressure and the reaction time for the first polymerization; the second polymerization conditions at least comprise the types and the amounts of the first olefin monomer and the first auxiliary agent, the reaction temperature, the reaction pressure and the reaction time of the first polymerization; and the first polymerization and the second polymerization are alternately reacted for a number of times. The setting conditions can be designed according to the experience of technicians, and can also be designed by simulating the polymerization reaction process through a computer; the design is preferably performed by computer simulation of the polymerization process and the experience of the skilled person is combined to make the final decision.
A stirring system is provided in each of the polymerization reactors of the first polymerization and the second polymerization, which may comprise one or more stirrers. Typically the stirrer should ensure that the reactants are able to operate under thorough mixing conditions.
According to the invention, through the process design, the first polymerization and the second polymerization are alternately subjected to polymerization reaction under two different reaction conditions and reaction systems, so that the molecular structure of the manufactured polymer is reasonably controlled, and a propylene copolymer product with designable performance and high added value is obtained.
In each step of controlling the accurate metering of the catalyst, the metering comprises the steps of stirring and circulating the catalyst premix in a metering tank and accurately metering by a diaphragm metering pump; the diaphragm metering pump replaces a piston with a specially designed and processed flexible diaphragm, and realizes reciprocating motion under the action of a driving mechanism to complete the suction-discharge process. Due to the isolation of the diaphragm, a structural isolation between the fluid being measured and the drive lubrication mechanism can be achieved.
A stirrer with a pipeline structure is arranged on a pipeline for conveying; the stirrer with the pipeline structure can make the liquid medium and the gas medium forcedly convect and uniformly mix, and the stirrer consists of two straight blades, so that the generated radial liquid flow speed is low. The two blades of the pitched blade agitator are turned 45 or 60 in opposite directions, thereby creating an axial flow.
The buffering comprises stirring and circulating the catalyst premix in a buffer tank, and adjusting the temperature of the premix and the pressure in the buffer tank.
The propylene polymerization catalyst is prepared in an intermittent preparation mode, when the catalyst in each batch is switched, the dynamic change of the reaction temperature and the internal pressure in the polymerization reactor is generally shown as the trend of descending firstly and then ascending, so that the polymerization reaction is caused to generate larger fluctuation, the operation difficulty is brought to the stable polymerization reaction condition in the production link, and under certain conditions, the production failure is caused due to the fluctuation of the polymerization condition, so that the probability of polypropylene production accidents is increased; therefore, the technical scheme of the invention improves the feeding method of the propylene polymerization catalyst, and firstly, the propylene polymerization catalyst and the solvent are uniformly mixed to obtain a catalyst premix; and then, continuously stirring the catalyst premix in a metering tank, a conveying pipeline and a buffer tank to ensure that the premix keeps a uniform component state, and simultaneously controlling the temperature and pressure conditions of the buffer tank to be consistent with the process conditions of the first process of the polymerization reactor, thereby reducing the influence of catalyst feeding on the process conditions of the polymerization reaction, realizing stable control of the polymerization reaction conditions and controlling the molecular structure and the performance of a polymerization product.
The catalyst premixing and the feeding mode of the premixing liquid under continuous stirring can be carried out by adopting a specially arranged feeding system of the propylene polymerization catalyst.
The catalyst feed system comprises: the material mixing tank is provided with a stirrer and is used for uniformly mixing the propylene polymerization catalyst and the solvent to obtain a catalyst premix; the inlet of the metering tank is connected with the outlet of the batching tank; the metering tank is provided with a stirrer for continuously keeping components of the catalyst premix liquid uniform; the inlet of the diaphragm metering pump is connected with the outlet of the metering tank and is used for metering the catalyst premix; the inlet of the buffer tank is connected with the outlet of the diaphragm metering pump, and the outlet of the buffer tank is connected with the polymerization reactor; the buffer tank is internally provided with a stirrer, a temperature controller and a pressure regulator; the stirrer is used for continuously keeping the components of the catalyst premix liquid uniform; the temperature controller and the pressure regulator are respectively used for regulating the temperature of the catalyst premix liquid and the pressure in the buffer tank; and the stirrer with a pipeline structure is arranged on a conveying pipeline connected between the diaphragm metering pump and the buffer tank and is used for continuously keeping components of the catalyst premix liquid uniform in the conveying process.
The stirrer with the pipeline structure comprises a stirring shaft penetrating through the mixing pipeline, a stirring impeller is detachably mounted on the stirring shaft, and one end of the stirring shaft extends out of the mixing pipeline to be connected with a driving device. The two mixing pipelines are longitudinally arranged in parallel, the bottom ends of the two mixing pipelines are respectively provided with an expansion pipe fitting, and a communication elbow pipe is arranged between the bottom ends of the two expansion pipe fittings; the pipe diameter of the expansion pipe fitting is larger than that of the mixing pipeline and the communicating elbow pipe. The driving device comprises a driving motor, and the driving motor is installed above the mixing pipeline through a bracket.
The feed system described can be adapted not only to the feed of propylene polymerization catalyst premix but also to the expanded control of homogeneous feed for similar suspensions.
Preferably, the metering tank comprises at least two metering tanks. Preferably, the metering tanks are connected in parallel. The metering tanks at least comprise two metering tanks, and different metering tanks are connected in parallel. This connection ensures that the suspension of the catalyst components enters the polymerization reactor in a continuous operation to participate in the reaction.
Preferably, a protection valve is arranged between the metering tank and the diaphragm metering pump. The protection valve can be arranged between the metering tank and the diaphragm metering pump, and the structural design can isolate the catalyst suspension from long-time contact between the diaphragm metering pump and influence the metering accuracy and the service life of the metering pump, and can avoid misoperation in production to influence the polymerization reaction.
Preferably, the stroke of the diaphragm metering pump is adjustable. The stroke of the diaphragm metering pump can be flexibly adjusted according to actual production requirements.
Preferably, the stirrer of the pipeline structure is a plurality of stirrers; the distance between the stirrers of two adjacent pipeline structures is smaller than 2m. On a conveying pipeline of the feeding system, a plurality of stirrers with pipeline structures are arranged according to the length of the pipeline; in order to ensure the effect of continuous stirring, the setting distance of the suspension can be adjusted according to the sedimentation property of the suspension and the length of the pipeline, and generally, the distance between the stirrers of the two adjacent pipeline structures is smaller than 2m.
The propylene polymerization catalyst comprises a main catalyst and a cocatalyst; wherein, the chemical structural formula of the main catalyst is shown as the following formula:
in the above, R 1 And R is 2 Are independently selected from C1-C20 alkyl, C3-C20 naphtheneA group and a C6-C20 aryl group; r is R 3 And R is R 4 The two groups are identical or different and are respectively and independently selected from one of hydrogen atoms, C1-C20 alkyl groups, C3-C20 cycloalkyl groups and C6-C20 aryl groups; x is selected from Cl, br, methyl or ethyl; m is selected from titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium; the cocatalyst comprises an organometallic aluminium compound; the ratio of the cocatalyst to the main catalyst is 200-800:1 in terms of mass ratio.
The chemical structural formula of the main catalyst is that a plurality of alkyl substituents are connected on a whole heterocycle; the catalyst with the structure can effectively catalyze ethylene to copolymerize with other alpha-olefins, ethylene to copolymerize with polar olefin monomers, propylene to copolymerize with other alpha-olefins and propylene to copolymerize with polar olefin monomers, and the prepared polymer has high catalyst activity and excellent copolymerization performance.
The main catalyst with the structure can be directly matched with the cocatalyst to catalyze olefin polymerization, or can be loaded and then matched with the cocatalyst for use, and the specific mode can be determined according to actual requirements.
Substituents are respectively connected to three hetero atoms of the main ring structure; the substituents are independently selected and are not limited to each other. In general, the R 1 And R is 2 Each independently selected from one of C1-C20 alkyl, C3-C20 cycloalkyl and C6-C20 aryl; the R is 3 And R is 4 Each independently selected from one of a hydrogen atom, a C1-C20 alkyl group, a C3-C20 cycloalkyl group and a C6-C20 aryl group.
According to the technical scheme, the non-metallocene catalyst is adopted as a main catalyst, the main structure of the non-metallocene catalyst is a complex containing more hetero atoms, and compared with a complex containing only a single hetero atom (such as oxygen, nitrogen and the like), the non-metallocene catalyst has more variability in structure and has larger adjustment space in the aspect of adjusting the structure and the performance of a polymer; for example, if a certain amount of higher alpha-olefin (such as 1-octene) is inserted into the polyolefin molecular chain to prepare a block copolymer, the structure and performance of the polyolefin are obviously changed, so that the density of the polymer is lower than that of common polyolefin, the glass transition temperature is low, the low temperature resistance is good, and the dispersibility, weather resistance, flexibility and processability are good. In addition, the coordination atoms of the main catalyst are nitrogen, nitrogen and silicon, the oxygen affinity of the central metal atom M of the main catalyst is weak, and the structure is easier to realize the copolymerization of olefin and polar monomer, so that the functional polyolefin material with excellent performance is synthesized. Meanwhile, the main catalyst has the advantages of good particle morphology, narrow particle size distribution and the like besides higher polymerization activity. The main catalyst is very suitable for the gas phase polymerization process and bulk polymerization process of propylene, and is especially suitable for the gas phase polymerization process.
In principle, the technical solution of the present invention may be to use a non-metallocene catalyst as its main catalyst for the polymerization reaction, preferably the main catalyst defined above. The main catalyst is also the earlier research result of the research team. See CN201611257991.7 for its preparation.
In the propylene polymerization catalyst used in the present invention, wherein the cocatalyst may be an organometallic aluminum compound; further, the organometallic aluminum compound may be selected from aluminum alkyls or aluminum alkyl hydrolyzates of aluminum alkyls, alkylaluminoxane; further, the cocatalyst is at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and methylaluminoxane.
When the main catalyst and the cocatalyst are used in a certain proportion, the catalyst can effectively catalyze propylene homopolymerization, propylene and ethylene copolymerization, acrylonitrile homopolymerization and propylene and acrylonitrile copolymerization, and a propylene copolymer with excellent comprehensive performance and high added value is obtained.
In the technical scheme of the invention, the main catalyst and the cocatalyst are matched for catalytic reaction, and the main catalyst and the cocatalyst can be directly matched for catalyzing olefin polymerization, or the main catalyst can be used with the cocatalyst after being preloaded. The loading mode of the main catalyst is not particularly limited, and the main catalyst may be loaded by a loading mode in the prior art.
Preferably, the solvent is selected from at least one of n-hexane, heptane or toluene.
The solvent includes a solvent used for premixing the catalyst and a solvent used for solution polymerization. Solution polymerization is a process in which monomers and catalysts are dissolved in an appropriate solvent to perform polymerization. The solvent chosen is generally an organic solvent, but may also be water, and may be determined by the nature of the monomer, initiator or catalyst and the polymer formed, and the use of the solution of the polymer produced. Common organic solvents include alcohols, esters, ketones, aromatic hydrocarbons (benzene, toluene), and the like; in addition, aliphatic hydrocarbons, halogenated hydrocarbons, cycloalkanes, and the like are also used. In choosing the solvent, the following factors are considered: 1) The effect of the solvent on the polymerization activity is taken into account. Solvents tend not to be absolutely inert, they induce decomposition of the initiator, and chain radicals also have chain transfer reactions with solvents. Both of these effects may affect the rate of polymerization and the molecular weight. The solvent has a greater influence in ionic polymerization, and the polarity of the solvent has a significant influence on the form and activity of the active ion pairs, the rate of polymerization, the degree of polymerization, the molecular weight and distribution thereof, and the chain microstructure. For copolymerization, especially ionic copolymerization, the polarity of the solvent can affect the reactivity ratio of the monomers, which in turn affects the copolymerization behavior, such as copolymerization composition, sequence distribution, etc. Therefore, careful selection is required in selecting the solvent. 2) Influence of solvent on the solubility properties and gel effect of the polymer. When good solvent is selected, homogeneous polymerization is adopted, if the monomer concentration is not high, the gel effect can not appear, and the normal kinetic rule of free radical polymerization is followed. When a precipitant is used, precipitation polymerization may be performed, and the gel effect is remarkable. The influence of the poor solvent is between the two, and the influence depth depends on the quality degree and concentration of the solvent. When there is gel effect, the reaction is automatically accelerated and the molecular weight is increased. When chain transfer occurs simultaneously with the gel effect, the molecular weight distribution will depend on the depth of influence of these two opposite factors. In order to ensure that the polymerization system is homogeneous during the reaction, the solvent chosen should have good solubility for the initiator or catalyst, the monomer and the polymer. Thus being beneficial to reducing the viscosity, slowing down the gel effect and leading out the polymerization reaction heat. If necessary, mixed solvents may be used. Meanwhile, the factors of good economy, easy recovery, convenient re-refining, no toxicity, easy commercial availability, low cost, convenient transportation and storage and the like are also required to be considered. The technical scheme of the invention comprehensively considers the factors, and can obtain better effect when the adopted catalyst system is required to carry out the polymerization reaction under the anhydrous and anaerobic condition, so that the solvent in the invention is preferably at least one of n-hexane, heptane or toluene.
The viscosity of the polymerization system is lower than that of bulk polymerization, the mixing and heat dissipation are easier, the production operation and the temperature are easy to control, and the evaporation of the solvent can be utilized to remove the polymerization heat.
When the copolymerization is carried out by a bulk polymerization method, the solvent is used only when the catalyst is dissolved.
As described above, the polymerization process is provided with a step of judging whether the set condition is reached, and if it is judged that the set condition is reached, the polymerization reaction is terminated, and a chain terminator is added to the reaction system to terminate the reaction.
Preferably, the first polymerization further comprises adding a first auxiliary agent; the second polymerization further comprises adding a second auxiliary agent; the first aid and the second aid each comprise a chain terminator; the chain terminator is ethanol solution of hydrochloric acid. The volume concentration of the ethanol solution of the hydrochloric acid is 5-15%.
The first auxiliary agent and the second auxiliary agent may be designed and adjusted according to the needs of the target polymer, and are not particularly limited herein.
Since solution polymerization itself has environmental problems, it is industrially difficult to use a polymer solution only by other polymerization methods or directly. The technical scheme of the invention also follows the principle.
The technical scheme of the invention aims to prepare the propylene copolymer with excellent comprehensive performance and high added value, and the adopted monomers are defined as follows: the first olefin monomer is selected from propylene; or a mixture of propylene and ethylene. Wherein the molar content of propylene in the mixture is more than or equal to 96 percent.
In the first polymerization stage, the first olefin monomer is a mixture of ethylene and propylene or propylene alone, and the ethylene or propylene is polymerized from polyethylene or ethylene and propylene; when the reaction conditions are switched to the second polymerization, the two ends of the ethylene polymer molecular chain or the two ends of the propylene polymer molecular chain are connected with the acrylonitrile unit for polymerization; when the reaction conditions are switched to the first polymerization, connecting two ends of an acrylonitrile unit to perform polymerization; and alternately connecting an ethylene molecule or a propylene molecule with the structure of the acrylonitrile unit, sequentially and circularly polymerizing until the polymerization is completed according to the set polymerization conditions, and adding a chain terminator to finish the reaction.
The catalyst system has high catalytic activity when being used for the copolymerization of ethylene, propylene and acrylonitrile, and can obtain the propylene copolymer with excellent comprehensive performance and high added value.
When judging that the condition of finishing the polymerization reaction is reached, adding a chain terminator through a first auxiliary agent or a second auxiliary agent inlet to stop the reaction, wherein the chain terminator adopts a coordination polar compound, and the reaction is stopped by adopting ethanol solution of hydrochloric acid in the technical scheme of the invention.
The polymer slurry or solution may flow from the first polymerization reactor; the effluent includes polymer and other components that need to be separated and recovered. The separation of the polymer may be effected using conventional separation means, for example, the polymer may be recovered from the effluent by coalescence with a non-solvent or the like.
Preferably, the reaction temperature and the reaction pressure of the first polymerization condition and the second polymerization condition are the same or different.
The first polymerization conditions are: the reaction temperature is 40-75 ℃, and the reaction pressure is 0.5-3.0 Mpa; further, the reaction temperature is preferably 40-45 ℃, 45-50 ℃, 50-55 ℃, 55-60 ℃, 60-65 ℃, 65-70 ℃ and 70-75 ℃; the reaction pressure is preferably 0.5-1.0 Mpa, 1.0-1.5 Mpa, 1.5-2.0 Mpa, 2.0-2.5 Mpa, 2.5-3.0 Mpa.
The second polymerization conditions are: the reaction temperature is 60-90 ℃, and the reaction pressure is 2.0-4.0 Mpa. Further, the reaction temperature is preferably 60-65 ℃, 65-70 ℃, 70-75 ℃, 75-80 ℃, 80-85 ℃ and 85-90 ℃; the reaction pressure is preferably 2.0-2.5 Mpa, 2.5-3.0 Mpa, 3.0-3.5 Mpa and 3.5-4.0 Mpa.
The polymerization reaction is required to be carried out in an anaerobic or hypoxic environment. Preferably, both the first polymerization and the second polymerization are carried out in an inert gas atmosphere. The inert gas atmosphere may be nitrogen or may be adjusted according to actual conditions.
The amount and concentration of the catalyst used in the first polymerization and the second polymerization may be the same or different, and may be specifically designed according to the requirements of the target product and the properties of the olefin monomer, and are not particularly limited herein.
The specific reaction times of the first polymerization and the second polymerization may be specifically designed according to the requirements of the target product and the properties of the olefin monomer, and are not particularly limited herein.
The invention also provides application of the propylene copolymer.
The molecular structure of the propylene copolymer can be designed according to the process requirement, and the acrylonitrile copolymerization component modifies the performance of the ethylene polymer or the propylene polymer in the form of an access molecular main chain, so that on one hand, the effective control of the molecular structure is ensured, namely the molecular structure can be designed, and on the other hand, the chemical modification mode also avoids the technical defects existing in the blending modification or reactor blending modification in the prior art, so that a technician can design a polymer product according to the target expectation and adjust the structure of polymer molecules through the control of the process condition, thereby obtaining the propylene copolymer with excellent comprehensive performance and high added value.
The invention also provides a compatilizer which comprises the propylene copolymer and is applied to the polyacrylonitrile and polypropylene blend to improve the compatibility of the polyacrylonitrile and the polypropylene blend.
The compatibility detection is to prepare the polypropylene and the polyacrylonitrile into a blend according to a proportion and then observe the phase distribution of the blend through an electron microscope.
The invention also provides an adhesive, which comprises the propylene copolymer and is applied to the adhesion of the polypropylene material and the polar polypropylene material so as to improve the adhesion force of the polypropylene material and the polar polypropylene material.
The adhesive force detection is to coat the adhesive on the surface of a metal substrate, and measure the peel strength after drying.
The invention also provides a photo-aging resistant polypropylene resin for outdoor products, which comprises the propylene copolymer.
The photo-aging detection is to put the material into an artificial aging box for accelerated aging, measure the change of the tensile strength before and after aging, and calculate the strength reduction rate.
The invention also provides antistatic polypropylene resin which comprises the propylene copolymer.
The antistatic properties are measured by measuring the surface resistivity of the material.
Further details are provided below by way of specific examples, wherein the performance test of the propylene copolymers prepared in each example was carried out using methods of detection conventional in the art. The preparation method of the main catalyst is shown in CN201611257991.7. In the following examples, R is directly used 1 、R 2 、R 3 、R 4 M and X define the structure of the procatalyst.
Example 1
The main catalyst adopts the chemical structural formula (II), wherein R 1 Phenyl group, R 2 =phenyl, R 3 =phenyl, R 4 Phenyl, M is titanium, X is Cl, in an amount of 5mg; the cocatalyst adopts methylaluminoxane with the dosage of 2g; toluene is adopted as the organic solvent, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: the polymerization temperature is 40 ℃ and the polymerization pressure is 3Mpa in a nitrogen environment, and the polymerization time is 30min each time; the second polymerization conditions were as follows: the polymerization temperature is 70 ℃ and the polymerization pressure is 2Mpa in a nitrogen environment, and the polymerization time is 10min each time; the cycle was alternated 3 times. The specific operation steps are as follows:
A. dissolving a main catalyst and a cocatalyst in a toluene solvent, uniformly mixing, and continuously stirring for standby;
B. adding toluene solvent into a polymerization reaction vessel, and controlling first polymerization conditions; introducing a first olefin monomer into a polymerization reactor at a flow rate of 2g/min, and dropwise adding a catalyst premix into the polymerization reactor under the condition of continuous stirring, wherein the polymerization reactor is polymerized under the stirring state;
C. controlling a second polymerization condition, dropwise adding 2g of a second olefin monomer into the reaction mixture, and dropwise adding the catalyst premix into a polymerization reactor under the condition of continuous stirring, wherein the polymerization reactor is used for polymerization under the stirring state;
D. Controlling a first polymerization condition, introducing a first olefin monomer into a reaction mixture at a flow rate of 2g/min, and dropwise adding a catalyst premix into a polymerization reactor under a continuous stirring condition, wherein the polymerization reactor is used for polymerization under a stirring state;
E. c and D, circularly executing the step C and the step D;
F. the reaction was terminated with an ethanol solution containing 10% hydrochloric acid, filtered, and the resulting polymer was washed 3 times with ethanol, and then vacuum-dried at 50℃for 24 hours, followed by performance test.
The performance of the propylene copolymer product prepared in the example is detected, wherein the acrylonitrile unit access content and the access position are measured by a 13C nuclear magnetic resonance method, and the result shows that the polymerization sequence of the acrylonitrile unit in the copolymer is mainly in the middle of a main chain, only a small amount of cyano units are positioned at chain ends, and the molar percentage content of the acrylonitrile unit access is 1.86%; the weight average molecular weight of the copolymer was measured by gel chromatography, and was 490000; the melt index was 19g/10min as measured according to ASTM D1238; commercially available polypropylene, commercially available polyacrylonitrile and the copolymer of this example were mixed in 45%:45%:10% of the components are melted and mixed to prepare a blend, and the phase distribution of the blend is observed by an electron microscope, so that the phase of the blend is uniformly distributed, and the compatibility of the blend is good; the copolymer sample was subjected to accelerated aging in an artificial accelerated aging oven for one month, the change in tensile strength before and after aging was measured, and the strength decrease rate was calculated to be 19.3%.
Example 2
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 =benzyl, R 2 =methyl, R 3 =benzyl, R 4 Benzyl, M is zirconium, X is Cl, in an amount of 7mg; the cocatalyst adopts triethylaluminum, and the dosage is 5.6g; toluene is adopted as the organic solvent, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: the polymerization temperature is 60 ℃ and the polymerization pressure is 2Mpa in a nitrogen environment, and the polymerization time is 25min each time; the second polymerization conditions were as follows: the polymerization temperature is 60 ℃ and the polymerization pressure is 3Mpa in a nitrogen environment, and the polymerization time is 8min each time; the cycle was alternated 4 times.
Performance test was performed on the propylene copolymer product prepared in the example, wherein the molar percentage of acrylonitrile units in the copolymer was 2.51%; the weight average molecular weight of the copolymer was measured by gel chromatography and found to be 37000; the melt index was measured according to ASTM D1238 at 21g/10min; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 14.8%.
Example 3
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 =cyclohexyl, R 2 =methyl, R 3 =cyclohexyl, R 4 =cyclohexyl, M is yttrium, X is Cl, in an amount of 6mg; the cocatalyst adopts trimethylaluminum, and the dosage is 1.2g; the organic solvent adopts n-hexane, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: the polymerization temperature is 50 ℃ and the polymerization pressure is 2.5Mpa in a nitrogen environment, and the polymerization time is 30min each time; the second polymerization conditions were as follows: the polymerization temperature is 80 ℃ and the polymerization pressure is 3Mpa in a nitrogen environment, and the polymerization time is 8min each time; the cycle was alternated 5 times.
Performance test was performed on the propylene copolymer product prepared in the example, wherein the molar percentage of acrylonitrile units in the copolymer was 2.23%; the weight average molecular weight of the copolymer was measured by gel chromatography and found to be 62000; the melt index was measured according to ASTM D1238 at 15g/10min; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 15.1%.
Example 4
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 Phenyl group, R 2 =phenyl, R 3 =phenyl, R 4 Cyclopentyl, M is neodymium, X is Cl, in an amount of 8mg; the cocatalyst adopts tri-n-hexyl aluminum, and the dosage is 6g; the organic solvent is heptane, 200ml; the first olefin monomer is 96% propylene and 4% ethylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: the polymerization temperature is 70 ℃ and the polymerization pressure is 1.5Mpa in a nitrogen environment, and the polymerization time is 20min each time; the second polymerization conditions were as follows: the polymerization temperature is 90 ℃ and the polymerization pressure is 4Mpa in a nitrogen environment, and the polymerization time is 5min each time; the cycle was alternated 2 times.
Performance test was performed on the propylene copolymer product prepared in the example, wherein the molar percentage of acrylonitrile units in the copolymer was 2.62%; the weight average molecular weight of the copolymer was measured by gel chromatography, and found to be 160000; the melt index was measured to be 32g/10min according to ASTM D1238; the strength decrease rate of the copolymer sample after the artificial accelerated aging was calculated to be 13.2%.
Example 5
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 =cyclopentyl, R 2 =methyl, R 3 =phenyl, R 4 Phenyl, M is rhodium, X is Cl, in an amount of 5mg; the cocatalyst adopts triisobutyl aluminum, and the dosage is 3g; toluene is adopted as the organic solvent, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: the polymerization temperature is 75 ℃ and the polymerization pressure is 0.5Mpa in a nitrogen environment, and the polymerization time is 20min each time; second PolymerThe conditions were as follows: the polymerization temperature is 85 ℃ and the polymerization pressure is 3Mpa in a nitrogen environment, and the polymerization time is 10min each time; the cycle was alternated 4 times.
Performance test was performed on the propylene copolymer product prepared in the example, wherein the molar percentage of acrylonitrile units in the copolymer was 3.11%; the weight average molecular weight of the copolymer was measured by gel chromatography and found to be 420000; melt index measured according to ASTM D1238 at 20g/10min; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 11.7%.
Example 6
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 =ethyl, R 2 =ethyl, R 3 =phenyl, R 4 Phenyl, M is vanadium, X is Br, in an amount of 7mg; the cocatalyst adopts triisobutyl aluminum, and the dosage is 5g; toluene is adopted as the organic solvent, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: the polymerization temperature is 65 ℃ and the polymerization pressure is 1Mpa in a nitrogen environment, and the polymerization time is 30min each time; the second polymerization conditions were as follows: the polymerization temperature is 75 ℃ and the polymerization pressure is 3Mpa in a nitrogen environment, and the polymerization time is 5min each time; the cycle was alternated 3 times.
Performance detection is carried out on the propylene copolymer product prepared in the example, wherein the mole percentage content of acrylonitrile units in the copolymer is 1.89%; the weight average molecular weight of the copolymer was measured by gel chromatography and found to be 350000; the melt index was measured according to ASTM D1238 at 21g/10min; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 18.2%.
Example 7
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 =isopropyl, R 2 =isopropyl, R 3 =phenyl, R 4 Methyl, M is nickel, X is Cl, in an amount of 6mg; the cocatalyst adopts methylaluminoxane with the dosage of 4.8g; toluene is adopted as the organic solvent, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile;the first polymerization conditions were as follows: the polymerization temperature is 45 ℃ and the polymerization pressure is 2.5Mpa in a nitrogen environment, and the polymerization time is 10min each time; the second polymerization conditions were as follows: the polymerization temperature is 65 ℃ and the polymerization pressure is 3Mpa in a nitrogen environment, and the polymerization time is 5min each time; the cycle was alternated 3 times.
Performance test was performed on the propylene copolymer product prepared in the example, wherein the molar percentage of acrylonitrile units in the copolymer was 4.97%; the weight average molecular weight of the copolymer was measured by gel chromatography, and found to be 140000; the melt index was measured according to ASTM D1238 at 35g/10min; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 4.7%.
Example 8
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 =2, 6-dimethylphenyl, R 2 =2, 6-dimethylphenyl, R 3 =2, 6-dimethylphenyl, R 4 Methyl, M is cobalt, X is Cl, in an amount of 6mg; the cocatalyst adopts methylaluminoxane with the dosage of 4.8g; toluene is adopted as the organic solvent, 200ml; the first olefin monomer is propylene; the second olefin monomer is acrylonitrile; the first polymerization conditions were as follows: the polymerization temperature is 60 ℃ and the polymerization pressure is 2Mpa in a nitrogen environment, and the polymerization time is 15min each time; the second polymerization conditions were as follows: the polymerization temperature is 70 ℃ and the polymerization pressure is 4Mpa in a nitrogen environment, and the polymerization time is 5min each time; the cycle was alternated 3 times.
Performance test was performed on the propylene copolymer product prepared in the example, wherein the molar percentage of acrylonitrile units in the copolymer was 3.81%; the weight average molecular weight of the copolymer was measured by gel chromatography and found to be 210000; the melt index was 29g/10min as measured according to ASTM D1238; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 8.3%.
Example 9
The polymerization process was the same as in example 1. The main catalyst adopts the chemical structural formula, wherein R 1 =2, 6-dimethylphenyl, R 2 =2, 6-dimethylphenyl, R 3 =2, 6-dimethylphenyl, R 4 Methyl, M is cobalt, X is Cl, in an amount of 6mg; the cocatalyst adopts methylaluminoxane with the dosage of 4.8g; toluene is adopted as the organic solvent, 200ml; the first olefin monomer is acrylonitrile; the second olefin monomer is propylene; the first polymerization conditions were as follows: the polymerization temperature is 70 ℃ and the polymerization pressure is 4Mpa in a nitrogen environment, and the polymerization time is 5min each time; alternately circulating for 3 times; the second polymerization conditions were as follows: the polymerization temperature is 60 ℃ and the polymerization pressure is 2Mpa in a nitrogen atmosphere, and the polymerization time is 15min each time.
Performance test was performed on the propylene copolymer product prepared in the example, wherein the molar percentage of acrylonitrile units in the copolymer was 6.58%; the weight average molecular weight of the copolymer was 163000 as measured by gel chromatography; melt index measured according to ASTM D1238 at 30.5g/10min; the strength reduction rate of the copolymer sample after artificial accelerated aging was calculated to be 7.6%.
Comparative example 1
The kind and amount of the main catalyst, the kind and amount of the cocatalyst, the kind and amount of the organic solvent, and the kind and amount of the first olefin monomer and the second olefin monomer are the same as those of example 3; the polymerization conditions were as follows: the polymerization temperature is 50 ℃ and the polymerization pressure is 2.5Mpa in a nitrogen atmosphere, and the polymerization time is 220min each time.
Comparative example 2
The kind and amount of the main catalyst, the kind and amount of the cocatalyst, the kind and amount of the organic solvent, and the kind and amount of the first olefin monomer and the second olefin monomer are the same as those of example 3; the polymerization conditions were as follows: the polymerization temperature is 80 ℃ and the polymerization pressure is 3Mpa in a nitrogen environment, and the polymerization time is 220min each time.
The above examples 1 to 9 are only specific examples for realizing the technical solution of the present invention, by using the above examples, propylene or propylene containing a small amount of ethylene as the first olefin monomer and acrylonitrile monomer as the comonomer are copolymerized under the alternative process conditions proposed by the present invention, by controlling the polymerization reaction to adapt to different reaction conditions in different processes, the polymerization process is switched according to the process design under different reaction conditions, thereby controlling the molecular structure of the polymer to grow according to the designed molecular chain, the content of the copolymerization component in the polypropylene copolymer prepared by the technical solution of the present invention is controlled, and can be adjusted according to the needs of the target product, and the copolymerization component is connected into the molecular chain of ethylene or propylene polymer in the form of molecular chain structure connection, the structure is stable, the composition of the molecular chain does not migrate with time, the high value-added propylene copolymer with excellent comprehensive properties can be obtained, and the properties of the polypropylene copolymer can keep the excellent properties for a long time, and has very good effects and application values. Meanwhile, the technical scheme of the invention ensures that the catalyst components introduced into the polymerization reactor are uniform and the temperature and pressure are consistent with those of the polymerization reactor by controlling the feeding method of the catalyst, reduces the influence of the catalyst feeding procedure on the polymerization reaction to the minimum extent, ensures that the process condition of the polymerization reaction is controlled, prepares the high-performance polyolefin with a designable molecular structure, improves the uniformity and comprehensive performance of the molecular structure of the product, and simultaneously can avoid the blockage of a feeding pipeline and improve the production efficiency.
The above comparative examples 1 and 2 use the same amount of charge and reaction time as in example 3, and only do not use the process route of alternating copolymerization, and it is apparent from the results of the propylene copolymer obtained therefrom that the polymerization sequence of the acrylonitrile unit and the polymerization sequence of the propylene unit in the propylene copolymer cannot grow according to the designed molecular structure when copolymerized under a single condition, and the resultant product is a simple combination of the polymerization sequence of the long-chain propylene unit and the polymerization sequence of the long-chain acrylonitrile unit due to the large difference in reactivity ratio therebetween, and it is difficult to form a molecular structure in which the polymerization sequence of the propylene unit and the polymerization sequence of the acrylonitrile unit alternately occur; therefore, the technical scheme of the invention adopts an alternate copolymerization process route to reasonably control the time and the molecular sequence arrangement state of the first olefin monomer and the second olefin monomer which are connected into the polymer molecular chain, and can obtain the copolymer with a designable molecular structure.
Further, the chain structure and sequence structure of the copolymer will directly affect various properties of the copolymer when the copolymer is used as a polymer material, such as mechanical properties, dielectric properties, thermal properties, and the like, and also will directly affect the selection of molding conditions. According to the invention, the chain end length and chain structure of the polymer are determined through gel chromatography, and characteristic fingerprint generated by nuclear magnetic moment energy level change in the molecule is distinguished through a nuclear magnetic resonance method, so that the structural information of the molecule is obtained; and (5) comprehensively analyzing and deducing the sequence structure of the high molecular chain through the acquired information. Through comparative analysis, the molecular chain sequences of example 3 and comparative examples 1 and 2, it can be judged that the order of molecular chain structure access to the molecular chain of the polymer prepared by the technical scheme of the present invention is stably controlled, and when the letter a represents the first olefin unit and the letter B represents the second olefin unit, the molecular chain structure thereof is basically represented as a block, and belongs to a special gradient sequence structure, which is schematically referred to as aaaaaaabbbaaaaabbbb. In the comparative example, the technical scheme of the invention is not adopted to alternately charge the comonomer, and after a plurality of monomers enter a reaction system together, the polymer with an unstable structure is randomly generated mainly through the reactivity ratio difference of a plurality of olefin monomers, the molecular structure is not controlled, and the performance of the polymer is also unstable.
Further, the propylene copolymer of example 7 of the present invention was formed into a sheet, and the surface resistivity thereof was measured to obtain a result of 5.6X10 8 Omega, has good antistatic property, and the molecular structure is connected into the molecular main chain in the form of chemical structure, so that the antistatic property of the polymer is not affected due to the migration of groups with time.
Further, the propylene copolymer of example 7 of the present invention was dissolved and coated on a metal substrate, and its peel strength was measured after drying, as a result, 25.3N/10mm, which showed excellent adhesion properties, and the molecular structure was incorporated into the molecular main chain in the form of a chemical structure, without affecting the adhesion of the polymer due to the migration of groups over time.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (22)
1. A propylene copolymer comprising a polymerized sequence of propylene units and a polymerized sequence of acrylonitrile units in its molecular backbone, said polymerized sequence of propylene units alternating with said polymerized sequence of acrylonitrile units having the structural formula:
Wherein, m ', n and n' are positive integers, m: n is 20-100:1, m': n' is 20-100:1;
the preparation method of the propylene copolymer comprises the following steps:
(1) Introducing a first olefin monomer into a polymerization reactor in the presence of a propylene polymerization catalyst to polymerize the first olefin monomer under first polymerization conditions;
(2) Introducing a second olefin monomer into the reaction mixture of step (1) in the presence of a propylene polymerization catalyst, and polymerizing under second polymerization conditions;
(3) Introducing a first olefin monomer into the reaction mixture of step (2) in the presence of a propylene polymerization catalyst, so that the first olefin monomer is polymerized under first polymerization conditions;
(4) Repeating the steps 2) and 3) for 2-5 times;
(5) Adding a chain terminator to terminate the reaction, and then filtering and washing to obtain the propylene copolymer.
2. The propylene copolymer according to claim 1, wherein the polymerized sequences of acrylonitrile units comprise a polymerized sequence located in the middle of the molecular chain and a polymerized sequence located at the end of the molecular chain; wherein the content of the polymeric sequence positioned in the middle of the molecular chain is larger than that of the polymeric sequence positioned at the end of the molecular chain.
3. The propylene copolymer according to claim 1, wherein the percentage of acrylonitrile units in the propylene copolymer is 1.0% to 5.0% in terms of molar ratio.
4. Propylene copolymer according to claim 1 or 2, characterized in that the propylene copolymer has a weight average molecular weight of 50000 ～ 1000000.
5. A propylene copolymer according to claim 3, characterized in that it has a melt index of 10 to 40g/10min, measured according to ASTM D1238 standard.
6. A process for the preparation of a propylene copolymer as claimed in any one of claims 1 to 5, characterized by comprising the steps of:
(1) Introducing a first olefin monomer into a polymerization reactor in the presence of a propylene polymerization catalyst to polymerize the first olefin monomer under first polymerization conditions;
(2) Introducing a second olefin monomer into the reaction mixture of step (1) in the presence of a propylene polymerization catalyst, and polymerizing under second polymerization conditions;
(3) Introducing a first olefin monomer into the reaction mixture of step (2) in the presence of a propylene polymerization catalyst, so that the first olefin monomer is polymerized under first polymerization conditions;
(4) Repeating the steps 2) and 3) for 2-5 times;
(5) Adding a chain terminator to terminate the reaction, and then filtering and washing to obtain the propylene copolymer.
7. The process according to claim 6, wherein in step (1), the propylene polymerization catalyst is introduced into the polymerization reactor as follows:
(11) Uniformly mixing a propylene polymerization catalyst and a solvent to obtain a catalyst premix;
(12) The catalyst premix is sequentially metered, conveyed and buffered and then is introduced into a polymerization reactor; wherein the metering, the conveying and the pre-mixing liquid components in the buffering process are controlled to be uniform, and the pressure in a buffer tank adopted in the buffering process is controlled to be the same as the pressure in the polymerization reactor.
8. The process of claim 6, wherein the first polymerization conditions and the second polymerization conditions are alternately performed in a spatial sequence in the same polymerization reactor; two reaction areas with independently controlled reaction conditions are arranged in the polymerization reactor; each of the reaction zones is provided with a catalyst feed system.
9. The process according to claim 6, wherein the first polymerization conditions and the second polymerization conditions are each alternately carried out in a spatial sequence in two polymerization reactors connected in series; each of the polymerization reactors is provided with a catalyst feed system.
10. The method of preparing according to claim 7, wherein the metering comprises metering the catalyst premix in a metering tank; the metering tank is equipped with a stirring cycle and is precisely metered by means of a diaphragm metering pump.
11. The method according to claim 7, wherein a stirrer having a pipe structure is provided in the pipe for transportation.
12. The method of claim 7, wherein buffering comprises agitating the catalyst premix in a buffer tank and adjusting the temperature of the premix and the pressure within the buffer tank.
13. The method of producing according to claim 6, wherein the propylene polymerization catalyst comprises a main catalyst and a cocatalyst; wherein,
the chemical structural formula of the main catalyst is shown as the following formula:
in formula II, R 1 And R is 2 Each independently selected from one of C1-C20 alkyl, C3-C20 cycloalkyl and C6-C20 aryl; r is R 3 And R is R 4 The two groups are identical or different and are respectively and independently selected from one of hydrogen atoms, C1-C20 alkyl groups, C3-C20 cycloalkyl groups and C6-C20 aryl groups; x is selected from Cl, br, methyl or ethyl; m is selected from titanium, zirconium, hafnium, vanadium, rhodium, iron, nickel, cobalt, neodymium, palladium or yttrium;
the cocatalyst comprises an organometallic aluminum compound; preferably, the organic metal aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum or methylaluminoxane;
The ratio of the cocatalyst to the main catalyst is 200-800:1 in terms of mass ratio.
14. The method according to claim 7, wherein the solvent is at least one selected from the group consisting of n-hexane, n-heptane and toluene.
15. The method of claim 6, wherein the chain terminator is an ethanol solution of hydrochloric acid.
16. The process according to claim 6, wherein the first olefin monomer is selected from one of a mixture of propylene and ethylene and propylene, preferably, the molar content of propylene in the mixture is not less than 96%; the second olefinic monomer is selected from acrylonitrile monomers.
17. The production method according to claim 6, wherein the reaction temperature and the reaction pressure of the first polymerization condition and the second polymerization condition are the same or different; the first polymerization conditions are: the reaction temperature is 40-75 ℃, and the reaction pressure is 0.5-3.0 Mpa; the second polymerization conditions are: the reaction temperature is 60-90 ℃, and the reaction pressure is 2.0-4.0 Mpa.
18. The method according to claim 6, wherein the first polymerization condition and the second polymerization condition are both reactions under an inert gas atmosphere.
19. A compatibilizer comprising the propylene copolymer of any one of claims 1 to 5 for use in a blend of polyacrylonitrile and polypropylene to increase its compatibility.
20. An adhesive comprising the propylene copolymer of any one of claims 1 to 5 for bonding a polypropylene material to a polar polypropylene material to improve the bonding strength thereof.
21. A photo-aging resistant polypropylene resin for outdoor products, characterized by comprising the propylene copolymer as defined in any one of claims 1 to 5.
22. An antistatic polypropylene resin comprising the propylene copolymer according to any one of claims 1 to 5.
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| US4577008A (en) * | 1984-06-27 | 1986-03-18 | The Standard Oil Company | Process for the production of acrylonitrile-propylene copolymers |
| CN101787158A (en) * | 2009-10-10 | 2010-07-28 | 深圳市科聚新材料有限公司 | Directly sprayed polypropylene material and preparation method thereof |
| CN104371060A (en) * | 2013-08-13 | 2015-02-25 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile resin with evenly-distributed copolymerization sequence |
| WO2016210419A1 (en) * | 2015-06-26 | 2016-12-29 | Florida State University Research Foundation, Inc. | Dry process method for producing electrodes for electrochemical devices and electrodes for electrochemical devices |
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|---|---|---|---|---|
| US4577008A (en) * | 1984-06-27 | 1986-03-18 | The Standard Oil Company | Process for the production of acrylonitrile-propylene copolymers |
| CN101787158A (en) * | 2009-10-10 | 2010-07-28 | 深圳市科聚新材料有限公司 | Directly sprayed polypropylene material and preparation method thereof |
| CN104371060A (en) * | 2013-08-13 | 2015-02-25 | 中国石油化工股份有限公司 | Preparation method of polyacrylonitrile resin with evenly-distributed copolymerization sequence |
| WO2016210419A1 (en) * | 2015-06-26 | 2016-12-29 | Florida State University Research Foundation, Inc. | Dry process method for producing electrodes for electrochemical devices and electrodes for electrochemical devices |
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